Art of making hydraulic cements, &amp;c.



nruran srar P TENT FTTJEQ WILLIAM E. HARDING, OF PHILADELPHIA, PENNSYLVANIA.

ART OF MAKING HYDRAULIC QENTS, &c.

No. scenes.

Specification of Letters Patent.

Patented Dec. 29, 1908.

Application filed April 30, 1968. Serial No. 480,163.

other processes involving the decompositionof minerals and the fritting or clinkering of the nonvolatile products of such-decomposition.

The production of Portland cement necessarilv involves the fritting or clinkering of an alkaline base, such as lime (CaO) with-an acid of the class typified by silica (SiO and alumina (A1 0,). Usually, the lime, silica, and alumina are all present in certain proportions, and thelimits of variation in the percentage of each are now well recognized in the art. As the constituent materials are not found in nature in a free state, they are commonly prepared for the clinkering process by the burning of raw materials containing compounds thereof in suitable proportions and free from too great admixture of objectionable materials or elements which might interfere with the processor deteriorate the quality of the cement product.

If the natural materials available do not contain the constituents in proper proportion, a suitably proportioned mixture may be prepared either by using dilierent materials, eac containing one or more desired constituents, or by combining a material containing too great a proportion of one constituent with another material containing too great a proportion of another constituent.

The lime is commonly obtained from material containing calcium carbonate (CaCO which is decomposed by heat into lime (Ca()) and carbon dioxid gas (C0,), and the silica and alumina are commonly obtained from materials in which they are found combined with water of crystallization,-which is driven ofi by the heat.

Commonly the raw material is natural rock containing 'vagying proportions of calcium carbonate an silica, commonly associated with alumina, magnesia, iron, etc.

Usually, lime rock, chalk, or similar material, containing a greater lime content than is necessary for Portland cement is used in connection with so-called cement rock, clay, or other material containing an excess of silica, the proportions being such that the mixture when calcined and 'lritted or clinloered, will consist of a compound containing tri-calcium silicate and aluminate.

According to the universal practice, these raw materials are finely ground and intimately mixed, either wet "or dry, prior to .heating them to drive of]? the carbon dioxid and water from the lime, silica, and alumina. The double process, first of decarbonizing the calcium carbonate and dehydrating the silica and alumina, and, second, frittin or clinkering the resulting lime, silica, an

alumina so that they may unite in the proper relation to form what is commonly supposed to be a solid solution" of calcium silicates, aluminates, etc., is now and alwa s has been performed by a single heat, bot when the burning is done in an upright kiln and when it is done ina rotary kiln. It has long been recognized that the upright kiln is not well adapted for clinkering and that the rotary kiln is uneconomical, and it was proposed to completely dry and calcine the material in an upright kiln and then clinker it in a rotary kiln; but prior to my invention this method has been found to be practically impossible, and no one has ever succeeded in applying it commerciall Moreover, the proposition has been dec ared unsound, be cause the rotary kiln re uircs such great heat at the lower end for c mkering that any amount which can be absorbed in calcining further u pared wit 1 the total unavoidable waste. The result has been that the single burning opera tion with continuous calcining and clinkering in .a rotary kiln has gradually become recognized and generally accepted as the standard modern method of making Portland eement, so that now practically all of the Portland cement made in this country is produced by this method, and the use of the upright kiln for Rosendale cement,

has been due mainly to the demand for a cheaper, lower grade cement and to the preexistence of the upright kiln plants and the expense involved in substituting rotary kilns.

My present invention consists of a method the kiln is insignificant as com" whereby the raw material instead of being l to a temperature commonly supposed to be calcined and clinkered at one heat, is subjected to two distinct burning operations in such manner and under such'conditions as to have proved highly practical and economical, as well as productive of a good quality of Portland cement clinker.

Heretofore, it has been supposed that the method of burning cement 1n a rotary kiln would be improved if the deearbonization of all of the materials were made perfect before any of it is exposed to a clinkering temperature, but according to my experience with my. process in which this is an easily obtainable condition, it is desirable that there be some uncalcined material, even though it be an extremely small percentage which remains to be decomposed in the rotary kiln, preferably so as to absorb heat at or near the region where the intensity ofthe applied heat begins to approach a temperature sufiicient to clinker fully calcined material, to the end that the material shall not be too fully clinkered at a point too far up the kiln, as this would result in subjecting the clinker to clinkering temperature for too long a time. In fact, the clinkering operation in the continuous feed rotary kiln is most easily accomplished where the decarbonizing or calcining reaction is prolonged so that it will be taking place to some extent at least at or near the time and place where the clinkering process commences, so that the two processes succeed each other or even overlap or intermingle in the sense that certain particles may be undergoing decarbonization at points not too remote from other )articles which are sintering or fritting to form the clinker. One reason for this may be that the clinkering operation, wherein the alkaline lime at high temperature unites with the acid silica and alumina, is, theoretically at least, an exothermic or heat evolving operation and, in any event, is one which does not involve appreciable absorption of heat, whereas the operation of driving oil the carbon dioxid from the calcium carbonate, though occurring at a lower tern erature, is an endothermic reaction whic does involve greatabsorptien of heat. It seems probable that a certain amount of the heat absorbing operation of driving oil carbon dioxid is beneficial, inasmuch as its refrigerating effect must tend to temper the heat evolving operation of clinkering, and if this had no other effect, it would tend to localize the clinkering zone nearer the discharge end of the kiln, and thus,

to shorten the time between beginning of clinkering and discharge of the material from the kiln. This may be of considerable importance, insomuch as clinkering is a critical operation so far as concerns time and temperature. When performed in a rotary kiln, it requires that the material be raised between 2500 and 3000 degrees Fahrenheit, in order that the union of the materials may be sufiiciently complete and yet the temperature must not be too high or too long continued, or the material will be what is technically known as overburned.

in any event, I find it is advantageous to have some carbon dioxid (C0,) evolved in the clinkerin kiln, and the initial percentage is preferably such that under the special conditions of use, the last remnant of the CO, is driven oil and the heat absorbing reaction terminated at the proper time to give the best results. Anadvantage of my method is that the initial percentage of uncalcined material necessary for this purpose in any given kiln, may be accurately predetermined.

For any given percentage, the distribution or region of activity of its heat absorbing reaction may be further controlled by adjusting the heaviness of the feed and the rate of its travel therethrough. in general, it may be said that in all cases the clinkering by my method will be more rapid than by the old method with the uncalcined rock.

In the preferred practice of my method wherein I use previously calcined n'iaterial containin only the required percentage of uncalcined rock, the work which the heat must do is similar in kind, though. less in amount than the work which is performed in the last 20 or 30 feet of a rotary kiln operat ing by the old process onuncaleined material, so that for the practice of my method,

the length of the kiln need be only that necessary to do the required amount of chemical. Work, plus the length necessary for heating up the materials to the calcining temperature. Hence, an old fashioned short kiln is amply adequate for my purposes, though a kiln to feet or more in length may be employed and is even desirable iircase the material employed for my purposes contains an exceptionally large percentage of un bu mud or artially burned material.

nother feature of my invention consists in regulating the supply of the material to the upper end of the kiln and the rate of feed therethrough, so that the feed shall be heavy; that is to say, so that the amount of material lying on the upturning side of the kiln shall be equal to or greater than the amount of such material commonly found in the ordinary rotary kiln process, where uncalcined rock is used.

Another feature of my invention consists in burning the coal at the ordinary rate employed for raw unealcined rock, or even at a. considerably higher rate, and then utilizing the resulting heat by increasing the heaviness of the feed and the rate of travel of the material to a point where the increased amount of material operated upon, compensates for the decreased work which. a given. volume repart of my process.

producer gas jets.

scenes quires. in this way thefull jet will supply no more heat than is necessary for the amount of material operated upon. This reuires that the rate of travel of the material down the kiln be at least two and preferably three, or even four times as great as in the case of raw, uncalcined rock, though in each specific case the precise ratio will depend somewhat upon the percentage of unburned rock in my mixture, the latter depending, of

course, upon how thoroughly and completely I burn the material in the upright kiln.

There is another feature of myinvention which probably tends to account for my success. in the earlier days when the advan tage of complete calcination in one burning and separateelinkering by anotherburning was first proposed, the jets used in the rotary kilns were either atomized oil jets or The latter has always proved difficult of use for clinkering operations, because of the low heat intensity of the flame. On the other hand, the oil jets as used in rotary kilns have always been proportioned and designed to produce a very intense heat which would necessarily overburn the clinker unless restrained in some way, as by a dominant heat absorbin reaction continuing far down the kiln. 1 believe that this is one of the reasons why no one has ever succeeded in using this intensely hot flame for clinkering, except in connection with previously uncalcined, raw materials, which could be manipulated so as to distribute the heat absorbing decarbonization of the lime,

to any extent.

One of the meritorious features of my invention consists in the discovery that one of the varieties of fuel and one of the forms of jet burner now in common use is suitable for the practical performance of the clinkering The fuel which I use is very finely pulverized and carefully dried gas coal carrying approximately 30% to. 38% volatile matter. This fuel is usedin connection with a low pressure diffuse burner of the McAuley type, supplied with air by a rotary fan. I prefer this to the high velocity jet of the Hurry and Seamans type, which is supplied from an air compressor, because with the low pressure type the flame is more localized at the-lower end of the kiln. Moreover, the fuel itself has a comparatively narrow range of temperature, Which extends entirely through the range of temperature to the above described effect of the carbon dioxid in the material in the upper portion of the. kiln.

It will be seen that the percentage of C0,, the nature of the fuel, the character and location of the jet, the heaviness of travel of the material, and the rate of the feed, are all factors which are governed and controlled with the view to preventing such excessive overburning of the clinker as would make my process impractical. Hence, the degree and'extent to which the one expedient must be utilized will depend upon the extent and effectiveness with which the others are utilized, and considerable variation and substitution'of one for the other to produce the same result will be possible and desirable under varying circumstances and conditions. It will be obvious that the present full disclosure of the various possible subsidiary or contributing factors will enable those skilled in the art to successfully utilize one or more of these factors to the exclusion. of the others.

In attempting any such variations, considerablecaution should be exercised, par ti'cularly in the matter of attempting to completely calcine the material before sub jecting it to the final heat in the rotary kiln, because the absence of carbonic acid gas in the material wonderfully facilitates the operation in the rotary kiln, and at the same time the heat is necessarily very intense. Hence, unless great care is exercised in prop erly tempering and controlling the action of the heat, as by insuring the presence of some uncalcined rock or some other adequate heat absorbing Work in the rotary kiln, the clinker may be overburned. In fact, the great facility with which completely decarbonized material becomes overburned in the rotary kiln, is one of the causes which has heretofore made the double burning operation practically impossible of successful performance, and it is with a view to controlling and term poring or localizing the clinkering, instead of with a view to facilitating it, that l have de vised my present process wherein i make adequate use of some and preferably of all of the herein described tempering factors.

I will now describe an illustrative application of my process as practiced with certain specific raw materials: h aw material con- 'taining a hi h percentage of calcium carbon- 'll'ltl it cheaper to use one-hall or cined, though it may be onion. desired. ln certain cases, the burning may be in accordance With the best practice lime burning, though for my purposes I two-thirds as much fuel, or else to charge and draw the kiln considerably faster, since the partial burning that can be thus eliected is suiiicient for my purposes. I

ln like manner, cement rock in fragments or lumps of the usual size may be calcined in any desired Way, preferably in an upright kiln charged with alternate layers of rock and coal in accordance with the practice in burning Rosendale cement. in certain cases Where the lime rock is completely calcined, the cement rock will be considerably underburned, While the cement rock is com pletely calcined, the lime rock is preferably underburned, though it will be understood that both varieties of roclr may be completely calcined, if desired.

In any event, the two kinds of rock are burned in different kilns, so that calcining operations may be independent and indeendently controlled. This makes it possile to independently control the amount of fuel and the duration and intensity of its combustion, so as to make the conditions in each kiln such as are most suited to the particular kind of rock burned in that kiln. Each kind of rock is charged into its kiln in layers, with a thin layer of coal over each layer of the rock. The amounts of material and proportions of the layers will vary according to the nature of the rock used and the completeness of the calcination desired.

The amount of coal per barrel of the product may vary from, say, pounds for soft rock up to or pounds for hard rock.

The cement rock may be burned so as to produce a product averaging about 15 to per cent. lime, 25 to 30 per cent. silica, and 8 to 14 per cent. alumina, With about 10 per cent. of uncalcined rock, at an expense of no more than about 26 to 30 pounds of coal per barrel. in order to burn the lime rook surliciently for my purposes, it is desirable to use somewhat more coal; but the amount of burned lime rock required is usually less than the amount of the cement roc r with Which it mixed, and the combined material may be produced on a consumption. of about 36 to 32 pounds of coal per bar l. Enough of the burned lime roclr is used to form a mi f g ime, silica, and alumina in L 1r hing; iully limeu Poi opulent, the teiial be r iinely taoroughly mixed. hLla ial may be cl nker ed in an n, wh ch need not e oi great 1. i 1 1 ietely car-omen,

a .linlrercd "r process. no cotor calcining the 10% ot unhui 0. stone u; heating and olinl citing; all ol it was found to he betrreen and 50 pmmds per hsrrcl. The lriln was rotated at sli .y greater speed than usu lthc how s. ol the feed on the upturmng side was greater than us ml. She result of this test shows a consumption of 80 to pounds oi' coal per l of the product, of which 30 to 95 pound; \\:F mm parativcly inexpensive coal costing; bout one-half as much as the c t of coal which would have been required if been done in the rotary l; 1. ized coal l t i about to per cent. or"; t e cost for melt-- ing similar cement by the old process, \x'lnirre in all the calcining is done in the rotary lrilu. The line grinding of the hard reel" 3' r r l the old process is more ciirpr-n tre th grinding of my partially or u'lu'illy columns material.

The particular grades of lime rock and ol' cement roclr and tho pzn'ticula :nuounh, oi coal required in connectio tnrouiilh pro specified shove merely by no v o of a specific case/o1 the iruciim. but it i l L i l o, uircd in th e l o tary [2 tin scenes as l have above indicated, the work to be done includes the heating up of the material followed by the heat absorbing operation of driving off the water and any remaining carbon dioxid from such ortion of the rock as has not been previous y calcined. Though the calcination involves great heat absorption and/is one of the most eiiective and easily applied expedients for tempering the process and preventing premature clinkering, it is not essential in all cases and it will be evident from the spirit of my prior disclosure,

that if the feed is made sufliciently heavy and the agitation sufliciently rapid, and if these are roperly proportioned to the rate of feed, the ength of the kiln, and the intensity of the flame, so that all of the heat which can be transmitted to the material while traveling the required. distance down the kiln, will be only suflicient to do the work of heating up the material to the clinkering temperature by the time it arrives within a suitable distance from the discharge end or outletin such case, the duration of the clinkering reaction may be redetermined and controlled even thou h t e work done by the heat consists main y in raising temperature of the materials without doing chemical work. y

One of the advantages in making a. -art of the preliminary work done by the in the rotary kiln consist in the decomposition of calcium carbonate is that the reactions within the kiln at the lower end and the various attendant visible phenomena are more nearly analogous to those to which the ordinary cement burner has become accustomed in his prior experiences with rotary kilns, and hence he can more easily learn to gage the situation and to properly vary theconditions in the practice of my new process. Another great advantage is that the driving on of the last remnants of.

the C0, from the calcium carbonate requires a disproportionate amount of fuel when accomplished in the upright kiln, whereas the conditions in the rotary kiln are. the best ossible for completely and cheaply comp eting this work and the attendant heat absorption is there an advantage for the various reasons ex lained above.

in certain cases w ere the mere heatin oi thoroughly calcined and dehydrate materials would not furnish sufficient preliminary work and heat absorption in the rotary kiln, either because of the great length of the kiln, the slowness of the feed, or the intensity of the heat, the presence of the uncalcined constituent or its equivalent is especially desirable. in any case other kinds of preliminary work requiring the absorption of heat may be used in com hination with or as a substitute for the calcining reaction. Among the other kinds of work suitable for this purpose may be mentioned the evaporation of free water eat raw material calculate introduced or remaining in the mixture, or preferably the dissociation of combined. water of crystallization from silica, alumina, iron said, or clay, in which they may be contained; or the distilling oil of potash, soda, or sulfurconipounds. These latter reactions are especially effective 'in preventing overburnmg, insomuch as most of them occur at or near the clinkering point and involve chemical absorption of relatively large amounts of heat per unit weight. Hence, though the quantities may be very small, the tempering effect may be very noticeable.

lVhere the chemical Work done in the rotary kiln is largely that of calcining of a remnant of calcium carbonate, this remnant may consist of a constituent either of the cement rock or of the lime rock. Where the lime rock and cement rock are calcined in se' arate kilns, it may be desirable to comp etely calcine the lime rock and to get the desired percentage of calcium carbonate by underburning. the cement rock.

In certain cases, the lime rock and the cement rock or other raw materials may be completely calcined and dehydrated in the upright kiln, and then ground and mixed in pro er proportions required for the Portland cement clinker. This material, re uirin practically no chemical work to be per orme in the rotary kiln, may then be modified or, as it were, loaded bythe addition of a certain amount of previously repared mixture of g to furnish the required amount of calcining or other heat absorbing ire-action in the rotary kiln. This furnishes a convenient method of standardizin the operations of the plant, since a standard raw mixture may be prepared which when added to the completely calcined mixture, will always give a standard, definite mixture to be acted upon by the heat in the rotary kiln. While this method of preparing the material is convenient and certain, it necessarily involves the expense of com leting calcination of the ma'or portion 0 the material in the uprig t kiln.

Hence, I prefer in actual ractice to underburn as uniformly as poss1 le in the upright kiln, so as to get an approximately uniform product, and then to correct unavoidable ture is not attempted or is imperfect, the rate .and heaviness of feed and the adjustmentjof flame and the amount of coal burned, may be varied so as to compensate for a considerable range of variation in the mixture.

So far as concerns the broader subject matter, all the steps of my process are independent of the specific form of the ap. aratus in which the operation is performed; ence, eX- cept as therein otherwise definitely specified, the claims for the process are not limited to the specific apparatus described in the speci fication. there is more or less definite. specification of apparatus, it will be understood that the ap paratus is referred to for the purpose of more easily defining the nature of the operation constitutin the process, rather than with a view to including any specific apparatus as a feature of my invention.

In certain of the claims I have referred to predetermining or adjusting certain factors of the operation of the clinkering kiln, as, for instance, the rate of supply of material and the rapidity ofrotation of the ldln, with res ect to the pitch, diameter, and length of t e kiln and to the distribution and intensity of the heat within the kiln andwith respect to the work which must be done upon the material to bring it to the clinkering tem er ature. In these cases the language is sue as might be taken to imply that those factors whlch are predetermined or adjusted are the only variable factors and that the factors with respect to which they are adjusted are and length of the kiln and t 1e distribution others.

and intensity of the heat within the kiln are equally convenient and desirable factors for variation or adjustment with reference to the 'l he work u hich must be done on the material to bring it to the clinkering temperature is, ofcourse, in all cases capable of variation by variation in the character of the constituents of the material. Hence, it will be understood that where certain of these factors are s ecified in the claims as variable or adjustab e with respect to certain other factors, such claims are to be considered as covering a process wherein any one or all of said. factors are varied, adjusted, or predetermined for the described purposes, with ireterence to any one or all of the other factors.

Lime rock and cement rock may be classed together for some purposes and separately for other purposes. In nature they are fire quently found in adjacent of the same In certain of the claims whereinscenes formation, and in certain cases they may -more or less overlap and merge into each objectionable efl ect on the components ol the Portland cement clinker to be made therefrom. The lime rock may be substantially pure calcium carbonate, or it may include rock having a smaller percentage of lime, provided the amount be in excess of" the proportions suitable for the manufacture of the desired quality of Portland cement clinker. Similarly, cement rock may be rock which contains within itself the proportions ohlime, silica, and alumina suitable for calcining and clinkering to make hydraulic cement, or it may include similar rock containing lime, silica, alumina, etc., but having the percentage of lime too small for the desired quality of cement.

I claim:

1. The improvement in the art of making Portland cement, which consists in burning a plurality of kinds of raw material independently, one kind capable of yielding a burned product containing a percentage of alkaline base greater than desired for the Portland cement clinker, and another kind capable of yielding a burned product containing a percentage of the acid salts greaterthan desired for Portland cement clinker; grinding said product and utilizing the same in proper proportions to form material containing the a lkaline base and the acid salts in the proportion required for the quality of cement desired; feeding said material into a rotary kiln; generating in said kiln a temperature sullicicnt to elfect the clinkering of the material at the lower end thereof; and predetcrminiug or adjusting the rate of supply of the materials and the rapidity of rotation of the kiln with respect to the pitch, diameter, and length of the kiln and to the distribution, quantity and intensity of the heat within the kiln and with respect to the work which must be done on the material to bring it to the clinkcring temperature, for the purpose of controlling the heaviness of the feed and the exposure oi the material to the heat and thereby coutrolling the clinkering reaction, substantially as described.

2. 'l he improvement in the art of making Portland cement, which consists in burning different qualities of rock by independent operations, the amount of fuel, its rate of combustion and the method and extent of its application being in each case determined and controlled with reference to the physical and chemical qualities of each respectively;

grimhng the product and preparing there-- 1:

lie)

from a mixture containing lime, silica, etc., in proportionssuitable for cement; feeding said material into a rotary kiln; generating in said kiln a temperature sufficient to efiect the clinkering of the material at the lower end thereof; and predetermining or adjusting the rate of'supply of the materials and the rapidity of rotation of the kiln with respect to the'pitch, diameter, and length of t e kiln and to the distribution, quantity and intensity of the heat within the kiln and with respect to the work which must be done on the material to bring it tothe clinkering temperature, for the purpose of controlling the heaviness of the feed and the exposure of the material to the heat and thereby controlling the clinkering reaction, substantially as described.

3. In the art of making Portland cement, the method which consists in separately calcining lime rockand cement rock by independently controlled methods suited to the different hysical and chemical qualities of the two kinds of rock; grinding the product and preparing therefrom a mixture containing lime, silica, etc., in pro ortions suitable for cement; subjecting sai materialto the action of heat in a region maintained at a temperature sufficient to effect the clinkering of the material and predetermining or adjusting the rate of supply of the material to said region and the rate of its travel therethrough and the resulting heaviness of feed and-extent of theexposure of the material with respect to the distribution, uantity and intensity of the heat within sai region and with respect to the work which must be done on the material to bring it to the clinkering temperature, for the purpose of controlhng the clinkering reaction, substantially as described.

4. In the art of making Portland cement,

the method which consists in separately calcining lime rock and cement rock by independently controlled methods suited to the different physical and chemical ualities of the two kinds of rock and to t e degree of calcination desired for each; rinding the product and preparing thererom a mixture containing lime, silica, etc., in proportions suitable for cement; feeding said material into a rotary kiln; generating in said kiln a temperature sufficient to effect the clinkering of the material at the lower end thereof; and predetermining or adjusting the rate of supply of the materials and the rapidity of rotation of the kiln with res ect to the pitch, diameter, and length 0 the kiln and to the distribution, quantity and intensity of the heat within the kiln and with res ect to the work which must be done on t e material to bring it to the clinkerin tem erature, for the purpose of control 'ng tfie heaviness of the feed and the exposure of the material tothe heat and thereby controlling the clinkering reaction, substantially as described.

5. The improvement in the art of making Portland cement, which consists in separatelyv calcining fragmental lime rock and cement rock by independent operations, the amount of fuel, its rate of combustion and the method and extent of its ap lication to the several varieties of rock, ein in each case determined and controlle with reference to the different qualities of the several varieties of rock and to the proportion of undissociated material desired in the product; grinding the product and pre-" ime, silica, etc., in proportions suitable for cement; and clinkering said material in a rotary kiln, for the purpose described.

6. The improvement in the art of making Portland cement, which consists in separately calcining fragmental lime rock and cement rock by independent operations, the amount of fuel, its rate of combustion and the method and extent of its ap lication to the several varieties of rock, being in each case determined and controlled with reference to the diflerent qualities of the several varieties of rock; grinding the product and preparin therefrom a mixture containing lime, si ica, etc., in proportions suitable for cement; feeding said material into a rotary kiln; generating in said kiln of rotation of the kiln with respect to the pitch, diameter, and length of the kiln and to the distribution, quantity and intensity of the heat within the kiln and with respect to the work which must be done on the material to bring it to the clinkering tern erature, for the ur ose of controlling the ieaviness of the eed and the ex osure of the-material to the heat and t ereby controlling the clinkering reaction, substantially as described. I

Signed at New York city, in the county of New York and State of New York, this twenty-eighth day of April, A. D. 1908.

. WILLIAM H. HARDING. Witnesses:

IRVING M. OBRIEGHT, ANITA BURKE. 

